Composition of matter and polymerization products thereof



plex synthesis.

Patented Oct. 30, 1945 COMPOSITION OF MATTER AND POLY- MERIZATIONPRODUCTS THEREOF Irving E. Muskat, Akron,

and Franklin Strain,

Norton Center, Ohio, assignors to Pittsburgh Plate Glass Company,Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. ApplicationJune 8, 1942, Serial No. 446,286

8 Claims. (01. 260-80) This invention relates to a new class of esterswhich are unsaturated carbonates having three carbonate radicals and twounsaturated groups. These compounds have the structure:

in which R1 and R4 are the radicals derived from unsaturated alcohols,preferably those containing three to five carbon atoms and anunsaturated linkage in an aliphatic chain such as allyl, chloralLvl,crotyl, methallyl, tiglyl, angelyl, chlorocrotyl a and p-ethylallyl andpropargyl alcohols, methyl vinyl carbinol, ethyl vinyl carbinol, and R1and R4 may, however, be the radicals derived from the alcoholscontaining six to ten carbon atoms such as cinnamyl, geranyl, linallyl,hexenyl, isopropylpropargyl and phenylpropargyl alcohols. I

R: and R3 in the above formula are organic radicals derived frompolyhydroxy compounds such as glycol, trimethylene glycol, propyleneglycol, tetramethylene glycol, di-, tri-, and tetraethylene glycols,di-, tri-, and tetrapropylene glycol, glycerine, the poly 'glycerols,erythritol, pentaerythritol, dextrose, cellulose, sucrose, etc.,resorcinol, phthalyl alcohol, pyrogallol, catechol, etc.

The symmetrical type esters in which R; is identical to R4 and in whichR2 is identical to R3, are of greater importance, being of less com-Intermediate compounds are first made by reacting sufficient quantitiesof unsaturated alcohol chloroformate with polyhydroxy compound to reactwith all except one of the hydroxy groups. The hydroxy groups have beenfound to be esterified substantially successively.

' For example, if glycol is treated withan equimolar quantity ofallyl'chloroformate the principal product will be allyl hydroxyethylcarbonate and only a small amount of glycol bis (allyl carbonate) will.be present. When glycerol is similarly esterified it was found that theprimary alcohol groups esterify quite readily while the secondary reactsless readily. Unsaturated partial esters of the hydroxy compounds whichhave more than three hydroxy groups may also be prepared. I

The reaction is co ducted by adding the unsaturated chloroformate inproper'proportion'to the polyhydroxy compound in the presence of analkaline agent such as pyridine or other cyclic tertiary amine or theoxide, carbonate, or hydroxide of an alkali metal or alkaline earthmetal. The reaction may be conducted in the presence of a suitablesolvent, such as benzene, carbon tetrachloride, petroleum ether,toluene, etc. Ordinarily the reaction is initiated at temperaturesbetween 0 C. and 20 C. but as the reaction approaches completiontemperatures of C. to C. may be advantageous and are usually effected byheating on a water bath.

Although frequently the reaction may be controlled to produce thedesired intermediate compounds in high yields, yet usually some of thecompletely esterified hydroxy comound is present. This may be separatedby washing out the solubl hydroxy compound with water or similar solventor by distillation in a vacuum. Generally, however, a small proportionof the completely esterified polyhydroxy compound is not objectionablesince it has chemical and physical properties very similar to the newesters. Accordingly, separation is not always necessary.

The intermediate compounds are then reacted with phosgene which couplestwo molecules of the intermediate hydroxy compound with a carbonatelinkage. The phosgene is introduced in gaseousor liquid form to theliquid intermediate which may contain a suitable solvent or diluent suchas benzene, ether, toluene, etc., in the presence of an alkaline agentsuch as pyridine. NaOH, CaCOs, etc. The resulting ester may be washedwith dilute hydrochloric acid and/ or water and freed of the morevolatile impurities, by heating at reduced pressures. I

Unsymmetrical variations of the new type esters may b prepared by firstsynthesizing the intermediate hydroxy esters such as allylZ-hydroxyethyl carbonate, methallyl 3-hydroxy propyl carbonate, etc. andthen converting the hydroxy ester into the corresponding chloroiormateby reaction with phosgene in a neutral solution and preferably attemperatures below +20 C. The chloroformate may then be mixed with anequimolal quantity of a different monohydroxy ester of an unsaturatedalcohol and a polyhydroxy compound. in the presence of an alkalinereactant. The unsymmetrical carbonates are thus produced.

The new carbonates are generally colorless liquids having relatively lowviscosity. They are quite stable over wide ranges of temperatures.Accordingly, they are useful as plasticizers, selvents, etc. The newcompounds polymerize readily in the presence of oxygen, hydrogenperoxide, organic peroxides, etc., especially when subjected to heat, orultra violet light.

Many new and valuable resin compositions may be prepared by polymerizingthe new chemical compounds. The monomeric or partially polymerizedesters may be used as coating or impregnating compositions with orwithout added solvent. Suitable thickening agents, plasticizers,pigments, dyes, etc. may be incorporated. Such materials ise usfiulin-the sprepa'ratian of water-prooied fabrics -or laminated sheets:useful as a construction material. The new compounds may also be castpolymerized to transparent sheets suitable for use aslglasssuhstitutes.Similarly, irregular shapes maylbe preparod. .Qdlored and otherdecorative objects may'be prepared by incorporating fil1e:s,:e'ix:.;:and by using fibrous fillers, composition with high impact strength maybe secured- Molding-powders containing monomer, partial polymer, 'ormixtures thereof with pigments, fillers etc may be used in directpressure molding or injection molding processes.

The preparation and polymerization oithe new mnre-tspecifioalldemonstrated my theioliowiag examples:

Example I 'A'miarture'or820 grams of ethylene glycol and Q36 items :01*pyridine was prepared and [cooled to (PE. With vigorousstirr'ingfiOBgrams of allyl oliloroformate were added 'slowly while-maintdining thetemperature betweenl) and C. by

m0! m me-138th. The-addition required 48 minutes. The-"mixture waswashed with three volumes-of water and separated into two liquid phases.By saturating the aqueous'layer with anhydrous sodium sulfate, 'a secondliquid phase precipitated. "Ihe watensolution .was then meted threetimes with :one-lhalf volume :of dwher. lheether was'evaporated'andtheresidue eomiiineiiwiththefraction edited out. 'Thisma- -burial-wasproven to be allyl 2=hydroxyethyl can bona'te. Dne "hundred or thiswater sol- 111m hydroxy esterwas suspended in 500 cc. of benzene and, 60grams pyridine. The mixture 'byflsulrhiir 1g the 'gas through :thesolution at-the 'Nte'df I5 millimoles per minute. The tempera-*tureremamed below 18 0. throughout the me motion. After the reactantswere combinedfthe 'benzene solution was washed with dilute hydroqihloricacid and water and then dried over an- 'hydrouswazm. The benzenesolution was heatiedto'evaporate the 0' benzene. A colorless liquid wasfound which had -arr-index of'rerraction of Flmil'and the formula:

'I'hree grams df'the ester was mixed with 0.15

grams of henzoylperoxide and heated at 75 C.

for ione'hour. I A "hard polymer wasiormed.

' Example which contained principally methallylhydroxy ethyl carbonateand smaller quantities of dimeth- :sllylecorla'onate and diethyleneglycol bis methal- .lulwnrbonate was treated with phosgene at .tem-

peratures maintained between +2'C. and +14 C. The phosgene was bubbledthrough the solution at the rate of 15 to 20 millimoles per minute.

The reaction mass was washed with diluted hydrochloric acid and withwater until neutral to litmus amd'then dried =over anhydrous Nae-S04.

The dried solution was heated withiigrams of activated charcoal at 3 to4 mm. until the ben- ,zene, the dimethallyl carbonate and other volatileimpurities were evaporated. A colorless liq- -uid was obtained havingthe structure:

:Eiee grams of the ester and 0.4 gram of acetone peroxide werethoroughly mixed and heated at 'I35'C. for one and one-half hours. Atransparient ssoiid having a ver slight :yellow molar was termed. I a

.ErmmpleJII mixture of salt and During the reaction'thetemperature washeld below +5 C. After standing overnight the mixture was again cooled'to 0 C. and a stream of phosgenefwas passetifirito the reaction-vesselat the 'rate of 20 mlllemoles,

per minute. After stirringforone hour themix- 'ture was heated for 'twohome on awaterbamh and "poured into an equal volume cf'ice water. Twohundred cc. of diethyl ether'was added and the 'two liquid phases wereseparated. The ether solution was washed with hydrochloric acid'and'withwater until neutral. The ether and other volatile impurities wereremoved 'by'heatin to 155 -'C. 'at a pressure or '3 mm. .A light yellowliguid 'was thereby produced which was believed to consist essentially'ofthe following ester.

The ester polymerized readily whenheated with 3% acetyl peroxide, forone hour at C.

This -application is a continuation-inflriaizt of Serial No. 403,703,filed July .23, 1941, y .Irving E. Muskatandli'ranklin Strain.

Although theinvention has been-described with respect to certainspecific.samples, it is not .111- tended that thedetailsof .the sameshall.be.construed as limitations upon the :scope'of tirednvention,vexceptto the extent incorporated in the-appendedclaims. I

We-claim: Y

1. .A new polymerizable compound having .the ,followingimolecularstructure:

wherein R1 is a radical corresponding to the radical R1 in thealcohol'RiOI-I, said alcoholbeing an unsaturated .monohydr'ic alcoholhaving from three to ten carbon atoms and having' "an unsaturatedcarbon-to-cai'bon linkage adjacent 2,367,934 I 3 the beta. carbon atomtherein, R: is a hydrocar- 4. A new polymerizable compound having thehon radical selected from' the class consisting of following molecularstructure:

divalent I saturated aliphatic hydrocarbon rad icals and divalentaromatic hydrocarbon radicals H and :c is a small whole number from 1 to4. 5 [CHFc CH' c0 cH-o ]=c 2. A new polymerizable compound having the 1following molecular structure: 5. A polymer of the compound defined by Qo claim 1. r g g I 8. A polymer of the compound defined by m claim 2. 3.A new polymerizable compound havin the A polymer f the compound d finedby following molecular ctructure: claim 3 o 8. A polymer of the compounddefined by ECH:=(?-CH210?-0CnHr-0Cfie-O-j g claim

